Detergent-compatible,fabric-softening compositions

ABSTRACT

AQUEOUS, DETERGENT-COMPATIBLE, FABRIC-SOFTENING COMPOSITIONS ARE DESCRIBED AS COMPRISING (A) A CATIONIC SOFTENING AGENT, (B) AN AMPHOTERIC SURFACTANT, AND (C) A MODIFIED POLYOLEFIN EMULSION.

United States Patent 3,749,691 DETERGENT-COMPATIBLE, FABRIC-SOFTENINGCOMPOSITIONS Thomas V. Kandathil, Racine, Wis., assignor to S. C.Johnson & Son, Inc., Racine, Wis.

No Drawing. Filed Dec. 31, 1970, Ser. No. 103,275 Int. Cl. Clld 3/28;D06m 15/26 US. Cl. 260-29.6 XA 11 Claims ABSTRACT OF THE DISCLOSUREAqueous, detergent-compatible, fabric-softening compositions aredescribed as comprising (A) a cationic softening agent, (B) anamphoteric surfactant, and (C) a modified polyolefin emulsion.

This invention relates to fabric-softening compositions. In one of itsmore specific aspects, this invention relates to aqueous,detergent-compatible, fabric-softening compositions.

Fabric-softening compositions (also referred to as fabric softeners)have been used in commercial and home laundry applications for the pastfew years. However, the presently available fabric-softeningcompositions generally require that they be added to the final rinse ofthe laundering process. If added directly to the wash cycle, thesecompositions do not produce the desirable or intended softening results.In addition, fabric softeners added to the Wash cycle tend to inteferewith the detergent and, as a consequence, the cleaning may not beadequate. Unless the laundering machine is equipped with a dispenser forthe fabric softener, a person must return to the laundry area to addthese fabric softeners to the rinse cycle. Thus, it will be recognizedthat a detergent-compatible, fabricsoftening composition would be ahighly useful product.

It is an object of this invention to provide a fabricsoftening'composition. Another object of this invention is to provide an aqueous,detergent-compatible, fabricsoftening composition. Still another objectof this invention is to provide a detergent-compatible, fabric-softeningcomposition having improved softening properties. Still another objectof this invention is to provide a process for softening fabrics with anaqueous, detergent-compatible, fabric-softening composition. Yet stillanother object of this invention is to provide fabrics softened with anaqueous, detergent-compatible, fabric-softening composition. Otherobjects of this invention will appear herein.

These and other objects are attained by the practice of this invention,one embodiment of which comprises providing an aqueous,detergent-compatible, fabric-softening composition comprising:

(A) a cationic softening agent; (B) an amphoteric surfactant; and (C) amodified polyolefin emulsion.

Another embodiment of this invention comprises providing a process forsoftening fabrics, wherein said process comprises contacting saidfabrics with the above-described aqueous, detergent-compatible,fabric-softening composition, which composition may be more specificallydescribed as comprising:

(A) from about to about 30 percent, by weight, of a cationic softeningagent;

(B) from about 1 to about 25 percent, by weight, of an amphotericsurfactant; and

(C) from about 0.25 to about 25 percent, by weight, of a modifiedpolyolefin emulsion.

Still another embodiment of this invention comprises providing a fabricsoftened with an aqueous, detergentcompatible, fabric-softeningcomponsition comprising:

(A) a cationic softening agent;

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(B) an amphoteric surfactant; and (C) a modified polyolefin emulsion.

When the fabric-softening compositions of this invention are added tothe wash cycle, the finished laundry is both clean and soft. Thisindicates that the detergent and fabric softener are not interferingwith each other. It is this type of interference which tends to resultin a substantial loss of detergent and softening capabilities.

An essential component of the fabric-softeners of this invention iscationic softening agent (that is, softening agents having an activecation). These agents contain one or two nitrogen atoms quaternized withreactants having groups such as sulfate, nitrate, nitrite, halide (e.g.,chloride, bromide, fluoride, or iodide), phospshate, and carbonate.

The cationic softening agents useful in this invention are thosederived, in part, from a fatty acid having at least 12 carbon atoms.Among the useful cationic softening agents are (a) the dialkylimidazolinium methosulfates, including thel-methyl-1-alkylamidoethyl-2-alkyl-imidazolinium methosulfates and (b)the dialkyl dimethyl quaternary ammonium chlorides.

Specific commercially available cationic softening agents falling incategory (a) include Varisoft 475 and Varisoft 222 from Varney ChemicalDivision of Northern Petrochemical Company, Armosoft AB from ArmourIndustrial Chemical Company, and Ammonyx 4080 from Onyx ChemicalCompany. Specific commercially available cationic softening agentsfalling in caegory (b) include Armosoft 2HT and Armosoft DC from Armour.

The cationic softening agents falling in category (3.) may also bedescribed as having the general formula:

wherein D is a divalent, non-amino, organic group having 1-24 carbonatoms and composed of elements from the group consisting of C, H, O, andN; D is a divalent organic group having 1-24 carbon atoms, composed ofelements from the group consisting of C, H, O, and N, and containing atleast one amino group; R is hydrogen, an alkyl group having 1-24 carbonatoms, or a cycloalkyl group having 1-24 carbon atoms (such as methyl,ethyl, propyl, butyl, hexyl, decyl, lauryl, myrisityl, palmityl,stearyl, tetracosanyl, cyclopentyl, cyclohexyl, oleyl, linoleyl); R isan alkyl group having 1-24 carbon atoms or an aralkyl group having 1-24carbon atoms (such as methyl, propyl, lauryl, stearyl, tetracosanyl,hydroxyethyl, hydroxypropyl, fluoromethyl, bromoethyl, benzyl,cinnamyl), with the provision that at least two of R and R are alkylgroups having at least 11 carbon atoms; A represents an anion; and Y andZ are each hydrogen or alkyl groups having 1-6 carbon atoms (such asmethyl, ethyl, propyl, pentyl, hexyl). A preferred D group is -CH CH anda preferred D group is amidoethyl.

Suitable anions include anions derived from sulfates, nitrates,nitrites, phosphates, carbonates, and halides (such as chloro, bromo,fiuoro and iodo).

Examples of useful cationic softening agents are disclosed in US. Pats.2,874,074 and 2,995,520; British Pat. 985,321; and McCutcheonsDetergents and Emulsifiers 1970 Annual.

An especially preferred cationic softening agent is 2- heptadecyl 1methyl 1 (stearyl amidoethyl)imidazolinium methosulfate.

The fabric-softening compositions of this invention generally comprisefrom about 5 to about 30 percent, by weight, of the cationic softeningagent. A preferred range is from about -25 percent, by weight. Blends ofcationic softening agents can be used.

Another essential component of these fabric softeners is an amphotericsurfactant. Because it contains an active cation and an active anion,this type of surfactant functions as a cationic surfactant in acid mediaand as an anionic surfactant in alkaline media. Amphoteric surfactants,in addition to contributing to the softening capability of these fabricsofteners, provide the following special advantages: have no adverseeffect on lightfastness or shade of dyestuffs; are resistant toyellowing during high temperature drying; produce no yellowing orrancidity of stored fabrics; gives excellent chemical stability over thepH range of these fabric softeners; and give antistatic effects onfabrics.

Amphoteric surfactants useful in the practice of this invention includethe complex fatty amido surfactants having the general formula:

wherein R is an alkyl group having 12-18 carbon atoms (such as lauryl,tridecyl, tetradecyl, pentadecyl, palmityl, heptadecyl, stearyl, ethyl,lauryl, oleyl, and linoleyl), R is a divalent aliphatic hydrocarbongroup having 2-5 carbon atoms (such as methylene, ethylene, propylene,butylene, 2-methylbutylene, and pentylene), R is a divalent aliphatichydrocarbon group having l-S carbon atoms (such as methylene, ethylene,propylene, butylene, 2-methylbutylene, and pentylene), and M is ahydrogen or an alkali metal (such as sodium, potassium, calcium, andlithium).

From the immediately preceding general formula, it will be recognizedthat R, R and R can be branched or unbranched and that R can besaturated or unsaturated.

Commercially available amphoteric surfactants useful in this inventioninclude Miranol CM (liquid) and Miranol DM (paste), both having theformula:

O CHzCOONa from Miranol Chemical Co., Inc.; Soromine AL and Soromine ATfrom GAF Corporation; and the Deriphat compounds from General Mills,Inc.

Useful amphoteric surfactants are disclosed in U .8. Pat. 2,528,378 andin McCutcheons Detergents and Emulsifiers 1970 Annual.

The fabric softeners of this invention generally comprise from about 1to about 25 percent, by weight, of the amphoteric surfactant. Apreferred range is from about 2.5 to about percent, by weight, A blendof amphoteric surfactants may be used.

A third essential component of these fabric softeners is a modifiedpolyolefin emulsion, preferably a modified polyethylene or polypropyleneemulsion. The term modified indicates that the polyolefin is at leastpartially oxidized and, with the aid of emulsifying agents, formed intoan emulsion. Depending upon the nature of the emulsifier used, themodified polyolefin emulsion may be nonionic, cationic, or anionic. Thefabric softeners of this invention may contain a blend of theseemulsions.

The modified polyolefin may contain functional groups, such as carboxyl,alkylamide, SulfOnic acid, and amide.

Examples of modified polyolefins which can be emulsified and used in thepractice of this invention include polyethylene; polypropylene; highdensity polyethylenes; and copolymers of polyethylene and acrylic acidor a substituted acrylic acid. These modified polyolefins arecommercially available from such sources as Eastman Chemical Products,Inc. (including the Epolene series) and Allied Chemical Company(including the AC series).

These emulsions generally have a solids content (including the modifiedpolyolefin) of about 10 to about 35 percent, by weight. A preferredrange is about 15 to about 30 percent, by weight.

If the modified polyolefin emulsions are prepared by using emulsifierswhich contain ethylene oxide units, these emulsifiers can contain up to16 moles of ethylene oxide.

The fabric-softening compositions of this invention generally comprisefrom about 0.25 to about 25 percent, by weight, of the modifiedpolyolefin emulsion. A preferred range is from about 0.5 to about 20percent, by weight.

These fabric softeners generally have a viscosity from about 50 to about3500 centipoises (measured using a Brookfield viscometer, RVF model, at20 r.p.m. with a #2 spindle) and a pH from about 3.5 to about 7.0.

Minor amounts (from about 0.001 to about 5.0 percent, by weight) ofoptional components may be used to enhance or provide particularcharacteristics to these fabric softeners. Examples of such optionalcomponents include viscosity-controlling agents, humectants, fluorescentwhitening agents, bactericides, perfumes, wetting agents, preservatives,anti-foaming agents, dispersing aids, and dyes.

The viscosity-controlling agents suitable for use in this invention areselected from the group consisting of metal salts of aliphatic,monocarboxylic acids having 14 carbon atoms; metal halides; and mixturesthereof. Examples of the acid salts are sodium, calcium, potassium,aluminum, and ammonium acetates; sodium, calcium, potassium, aluminum,and ammonium propionates; sodium, calcium, potassium, aluminum, andammonium formates; and sodium, calcium, potassium, aluminum, andammonium butyrates. Examples of the metal halides are sodium, calcium,potassium, aluminum, and ammonium chlorides; sodium, calcium, potassium,aluminum, and ammonium bromides; sodium, calcium, potassium, aluminum,and ammonium iodides; and sodium, calcium, potassium, aluminum, andammonium fluorides. A mixture of these agents may be used. A preferredviscosity-controlling agent is sodium chloride.

Various humectants may be used to improve the water absorbency of thefabrics treated with these fabric softeners. Examples of such humectantsare glycerin, polymethylene glycols having 26 carbon atoms (such asethylene, trimethylene, tetramethylene, pentamethylene, andhexymethylene glycols) and mixtures thereof. An especially preferredhumectant is ethylene glycol.

Another optional component is a fluorescent whitening agent to improvethe apparent whiteness and brightness of the cleaned and softenedfabrics. Examples of suitable fluorescent whitening agents are sold bySandoz, Inc., under the trade designation Sandoz TH-40; by GAFCorporation under the trade designation Blancophore; by AmericanCyanamid under the trade designation Calcofluor; by Geigy ChemicalCompany under the trade designation Tinopal; and by Ciba under the tradedesignation Uvitex. Blends of these agents may be used.

For an average load (3-5 pounds) of clothes to be washed and softened,from about one-half to about ten ounces of these fabric softeners can beadded to the wash cycle of an automatic washing machine. The specificamount to be added will necessarily depend upon such variables as thewashing condition and the amount of clothes to be washed and softened. Apreferred amount of fabric softener is from 1-5 ounces.

The fabric softeners of this invention are stable (i.e., do not separateinto phases in the container) for periods up to 3 months and longer.

A useful procedure for preparing the fabric-softening compositions ofthis invention is as follows: With mild agitation, the amphotericsurfactant is added to warm water (at least 90 F.). While continuing theagitation, the warm (at least 90 F.) cationic softening agent is addedto the surfactant-water blend. Finally, the modified polyolefin emulsionis added to the surfactant-watersoftening agent blend. Optionalcomponents can be added while cooling the final blend to roomtemperature.

The compositions of this invention soften fabrics containing fibers ofvarious types-such as cellulosics (e.g., cotton), and synthetics.Examples of synthetic fibers include polyesters (such as Kodel polyestersold by Eastman Chemical Products, Inc., and Dacron polyester sold byDuPont), and polyamides (such as nylon).

If desired, these fabric softeners can be added to the rinse cycle andequivalent softening will be obtained as when added to the wash cycle.

A preferred method of using these fabric softeners in an automaticwashing machine is to fill the wash tub with about two inches of waterand then add the fabric softener. After the addition of fabric softeneris completed and, as the wash tub is being filled with the remainingwater, the laundry is placed in the machine and then the detergent isadded.

The following standard test may be used to demonstrate that the fabricsofteners of this invention do provide (1) softness in the presence ofdetergents and (2) improved softness over other softening compositions:

Two laundry bundles (A and B) of about 4 pounds each and containing suchitems as Turkish towels (which are good exhibitors of softness), pillowcases, shirts, etc., are prepared. Bundle A is washed with detergent,but no fabric softener, in an automatic washing machine. Bundle B iswashed in an identical manner, but with about 3 /2 ounces of a fabricsoftener of this invention being added during the wash cycle. A panel of-12 members is then asked to determine the difference in softnessbetween bundles A and B.

The above standard test may be altered by adding, during the wash cycle,a prior fabric softener (that is, not one of this invention) to bundleA. The panel is then asked to determine the difference in softnessbetween bundles A and B.

This invention will be further illustrated by the following examples ofpreferred embodiments. However, it will be understood that theseexamples are included for purposes of illustration and are not intendedto limit the scope of this invention.

Unless otherwise indicated, all percentages are by In the aboveexamples: The blue dye is an oil-soluble blue dye. The anti-foamingagent is a 10 percent silicone anti-foaming agent. 31-6 is a dyeformulation consisting of 99.33 percent isopropyl alcohol and 0.67percent of the oil-soluble blue dye. 126-2" is an oxidized polyethyleneemulsion consisting of 69.092 percent water, 20.000 percent polyethylene(sold by Allied Chemical Company under the trade designation AC-629),5.000 percent nonylphenoxypoly(ethyleneoxy)ethanol, 5.000 percentdiethylene glycol, 0.708 percent of a 45% potassium hydroxide solution,and 0.200 percent of a 37% formaldehyde solution.

While laundry bundles of clothing are being laundered in an automaticwashing machine, the above eight compositions are added during the washcycle. The laundering is completed, and the clothes are then dried. Theclothes are clean, bright-looking, and soft. There is no interferencebetween the detergent and the softener.

Thus, it will be recognized that the fabric-softeners of this inventionpermit the user to obtain softness in the presence of detergents anddetergency in the presence of softness.

Although this invention has been described in detail with particularreference to preferred embodiments thereof, it will be understood thatvariations and modifications can be effected within the spirit and scopeof this invention as described hereinabove and as defined in theappended claims.

I claim:

1. An aqueous, detergent-compatible, fabric softening compositioncomprising:

(A) from about 5 to about 30 percent, by weight, of a cationic softeningagent containing one or two quaternized nitrogen atoms and being derivedin part from a fatty acid having at least 12 carbon atoms;

(B) from about 1 to about 25 percent, by weight, of an amphotericsurfactant having the general formula:

weight. N-E-Y EXAMPLES 1-8 R 0% A The following eight fabric-softeningcompositions are prepared to contain the percentages shown of eachcomponent: DR Z Percent in- Component Example 1 ExampleZ ExampleBExample4 Examplefi Example6 Example7 Example 8 Sodium chloride 0.200 0.200 0.200 0. 200 0. 200 0.200 72. 248 72. 298 72. 438 72. 488 72. 72.

Fluorescent whitening agent 0.200 0.200 0. 200 0. 200 0.200 0.200Anti-foaming agent 0. 050 0.050 0.050 31-6 0.300 0.300 126- 4. 000 4.000 4. 000 4. 000 4. 000 4. 000 Ethylene glycol 1.000 1.000 1 000 1. 0001.000 1.000 Peri e 0.300 0.300 0.300 0.300 0.300 0.300

Total 100.000 100.000 100. 000 100. 000 100. 000 100.000

wherein D is -CH CH D is amidoethyl; R is hydrogen, an alkyl grouphaving 124 carbon atoms, or a cycloalkyl group having 1-24 carbon atoms;R is an alkyl group having 1-24 carbon atoms or an aralkyl group having1-24 carbon atoms, with the provision that at least two of R and R arealkyl groups having at least 11 carbon atoms; A represents an anion; andY and Z are each hydrogen or alkyl groups having 1-6 carbon atoms.

3. A composition as defined by claim 1 wherein R is methylene and each Mis sodium.

4. A composition as defined by claim 1 wherein said polyolefin emulsionis a polypropylene emulsion.

5. A composition as defined by claim 1 wherein said cationic softeningagent is Z-heptadecyl-l-methyl-l-stearylamidoethylimidazoliniummethosulfate.

6. A composition as defined by claim 1 wherein said emulsion is apolyethylene emulsion.

7. An aqueous, detergent-compatible, fabric softening compositioncomprising:

(A) from about 5 to about 30 percent, by weight of a cationic softeningagent containing one of two quaterm'zed nitrogen atoms and being derivedin part from a fatty acid having at least 12 carbon atoms;

(B) from about 1 to about 25 percent, by weight, of an amphotericsurfactant having the general formula:

CH1 t 9H2 R- J-I i-R OM ofim-oo OM wherein R is an alkyl group having12l8 carbon atoms, R is an aliphatic hydrocarbon group having 2-5 carbonatoms, R is an aliphatic hydrocarbon group having 1-5 carbon atoms, andeach M is hydrogen or an alkali metal;

(C) from about 0.25 to about 25 percent, by weight, of a polyolefinemulsion, said polyolefin being selected from the group consisting ofpolyethylene and polypropylene and being at least partially oxidized;

(D) from about 0.001 to about 5 percent, by weight, of aviscosity-controlling agent selected from the group consisting of metalsalts of aliphatic, monocarboxylic acids having 1-4 carbon atoms; metalhalides; and mixtures thereof;

(E) from about 0.001 to about 5 percent, by weight,

of a fluorescent whitening agent; and

(F) from about 0.001 to about 5 percent, by weight, of a humectantselected from the group consisting of polymethylene glycols having 2-6atoms, glycerin, and mixtures thereof.

8. A composition as defined by claim 7 wherein said cationic softeningagent is Z-heptadecyl-l-methyl-l-stearyl amidoethylimidazoliniummethosulfate.

9. A composition as defined by claim 8 wherein said polyolefin emulsionis a polyethylene emulsion.

10. A composition as defined by claim 7 wherein saidviscosity-controlling agent is sodium chloride.

11. A composition as defined by claim 7 wherein said humectant isethylene glycol.

References Cited UNITED STATES PATENTS 3,537,993 11/1970 Coward et a1.252-8.75 3,245,831 4/ 1966 Shippee 117-1395 2,528,378 10/1950 Mannheimer252542 X 3,509,049 4/1970 Zweidler 2528.8 X 3,033,704 5/1962 Sherrill etal 252106 X 3,451,927 6/1969 Tune 2528.8 X

HERBERT B. GUYNN, Primary Examiner U.S. Cl. X.R.

117139.5 A, 139.5 CQ; 2528.75, 8.8, 89, 542, 547; 26029.6 MN

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 9, 9 LDated July 31, 1973 I r1 ventor(s) Thomas V. Kandathil I g It, iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

In Column 1, line 28, change "intefere" to "interfere".

In Column 1, line 71, change componsition to composition.

In Column 2, line 29, change caegory to category.

In Column 2, lines 71 -72, and Column 3, lines 58-59, DetergentsEmulsifiers 197Q Annual should be set off as a title.

In Column 3, line 63, change the comma after "weight" to a period.

In Claim 5, line 3, and Claim 8, line 3, change amidoethylimidazoliniumto amidoethyl -im idazo1inium.

In Claim 7, line 4', change of to or.

In Claim 9, line '1, change Claim 8 to Claim 7.

Signed and sealed this 9th day of April 1971;.

(SEAL) Attest:

EDWAP I-I.FLETCPER,JR I C MARSHALL DANN Attesting Officer Commissionerof Patents FORM PC4050 USCOMM-DC 60376-P69 U.S. GOVERNMENT PRINTINGOFFICE I919 0-368-334,

